U.S. patent application number 16/324114 was filed with the patent office on 2019-06-06 for kesterite material of czts, cztse or cztsse type.
This patent application is currently assigned to HALDOR TOPSOE A/S. The applicant listed for this patent is HALDOR TOPSOE A/S. Invention is credited to Soren DAHL, Jesper NERLOV, Niels Christian SCHJODT.
Application Number | 20190172711 16/324114 |
Document ID | / |
Family ID | 59745917 |
Filed Date | 2019-06-06 |
United States Patent
Application |
20190172711 |
Kind Code |
A1 |
SCHJODT; Niels Christian ;
et al. |
June 6, 2019 |
KESTERITE MATERIAL OF CZTS, CZTSe OR CZTSSe TYPE
Abstract
A method of producing a kesterite material of CZTS, CZTSe or
CZTSSe type, including the steps of: a) preparing an acidic
solution by dissolving copper and zinc salts in water in desired
molar ratio, b) preparing a basic solution by dissolving an alkali
metal stannate together with an alkali metal carbonate or an alkali
metal hydrogen carbonate or an alkali metal hydroxide or a
combination thereof, and optionally with an alkali metal selenate
or an alkali metal selenite or a mixture thereof, c) carrying out a
precipitation reaction by mixing the acidic and the basic solution,
d) drying the precipitate thereby providing a precursor for the
kesterite material, and e) sulfurizing the precursor of step d to
provide the kesterite material. Also, a precursor for a kesterite
material of CZTS, CZTSe or CZTSSe type.
Inventors: |
SCHJODT; Niels Christian;
(Hvalso, DK) ; DAHL; Soren; (Hillerod, DK)
; NERLOV; Jesper; (V.ae butted.rlose, DK) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
HALDOR TOPSOE A/S |
Kgs. Lyngby |
|
DK |
|
|
Assignee: |
HALDOR TOPSOE A/S
Kgs. Lyngby
DK
|
Family ID: |
59745917 |
Appl. No.: |
16/324114 |
Filed: |
September 1, 2017 |
PCT Filed: |
September 1, 2017 |
PCT NO: |
PCT/EP2017/071994 |
371 Date: |
February 7, 2019 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01L 21/02535 20130101;
C01B 19/002 20130101; C01P 2004/62 20130101; H01L 31/0326 20130101;
C01P 2006/40 20130101; C01G 19/006 20130101; C01P 2002/77 20130101;
C01P 2004/64 20130101 |
International
Class: |
H01L 21/02 20060101
H01L021/02; C01B 19/00 20060101 C01B019/00; C01G 19/00 20060101
C01G019/00; H01L 31/032 20060101 H01L031/032 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 7, 2016 |
DK |
PA 2016 00601 |
Claims
1. A method of producing a kesterite material of CZTS, CZTSe or
CZTSSe type, comprising the steps of: a) preparing an acidic
solution by dissolving copper and zinc salts in water in desired
molar ratio, b) preparing a basic solution by dissolving an alkali
metal stannate together with an alkali metal carbonate or an alkali
metal hydrogen carbonate or an alkali metal hydroxide or a
combination thereof, and optionally with an alkali metal selenate
or an alkali metal selenite or a mixture thereof, c) carrying out a
precipitation reaction by mixing said acidic and said basic
solution, thereby obtaining a precipitate, d) washing and heat
treating said precipitate thereby providing a precursor for the
kesterite material, and e) sulfurizing the precursor of step d to
provide the kesterite material.
2. The method according to claim 1, wherein the salts used for the
acidic solution are nitrates, halides, sulfates, carboxylates or
combinations thereof.
3. The method according to claim 1, wherein the copper salt is
copper (II) nitrate and the zinc salt is zinc (II) nitrate.
4. The method according to claim 1, wherein said acidic solution
further comprises nitric acid.
5. The method according to claim 1, wherein said alkali metal
stannate comprises Na.sub.2SnO.sub.3 and/or K.sub.2SnO.sub.3 in
hydrated or anhydrous form
6. The method according to claim 1, wherein said basic solution
further comprises selenium in the form of an alkali metal selenate
and/or an alkali metal selenite.
7. The method according to claim 1, wherein the step of sulfurizing
comprises subjecting the precursor to a sulfur comprising gas at a
temperature above room temperature.
8. The method according to claim 7, wherein said sulfur comprising
gas is one or more of the following: H.sub.2S, elemental sulfur in
gaseous state (S.sub.2--S.sub.8), COS, CS.sub.2organic sulfur
compounds.
9. The method according to claim 8, wherein said organic sulfur
compounds are CH.sub.3SH and/or CH.sub.3SSCH.sub.3.
10. The method according to claim 7, wherein said sulfur comprising
gas further comprises selenium.
11. The method according to claim 1, further comprising the
following steps between steps d) and e): grinding the precursor for
the kesterite material obtained by step d), dispersing said grinded
precursor in a liquid, thereby obtaining a slurry, depositing a
thin layer of the slurry onto a substrate, and optionally, drying
said thin layer.
12. The method according to claim 11, wherein the step of
dispersing said grinded precursor in a liquid comprises wetting and
dispersing said grinded precursor in a liquid using polymeric
wetting and/or dispersion agents.
13. The method according to claim 1, further comprising the
following steps subsequent to step e): grinding said kesterite
material, dispersing said grinded kesterite material in a liquid,
thereby obtaining a slurry, depositing a thin layer of the slurry
onto a substrate, optionally, drying said thin layer, and
optionally, heat treating such thin layer.
14. The method according to claim 1, wherein the step of dispersing
said grinded kesterite material in a liquid comprises wetting and
dispersing said grinded kesterite material in a liquid using
polymeric wetting and/or dispersion agents.
15. A precursor material for a kesterite material of CZTS, CZTSe or
CZTSSe type, where said precursor material is substantially sulfur
free and wherein powder XRD shows that the precursor material
comprises a Zn[Sn(OH).sub.6] phase and/or a Cu[Sn(OH).sub.6] phase
and/or a mixed {Cu, Zn}[Sn(OH).sub.6] phase.
Description
FIELD OF THE INVENTION
[0001] Embodiments of the invention generally relate to a method of
producing a kesterite material of CZTS, CZTSe or CZTSSe. The
invention moreover relates to a precursor material for a kesterite
material of CZTS, CZTSe or CZTSSe type.
BACKGROUND
[0002] Kesterite materials of CZTS (copper zinc tin sulfide) type,
of CZTSSe (copper zinc tin selenide sulfide) or CZTSe (copper zinc
tin selenide) type are semiconducting compounds which have received
increasing interest since the late 2000s for applications in solar
cells. Kesterite materials of CZTS, CZTSe or CZTSSe types offer
favorable optical and electronic properties similar to CIGS (copper
indium gallium selenide) making them well suited for use as a
thin-film solar cell absorber layer. However, unlike CIGS materials
and other thin films such as CdTe, CZTS, CZTSe or CZTSSe are
composed of only abundant and non-toxic elements. Concerns with the
price and availability of indium in CIGS and tellurium in CdTe, as
well as toxicity of cadmium have been a large motivator to search
for alternative thin film solar cell materials.
[0003] CZTS, CZTSe or CZTSSe type materials may be prepared by a
variety of vacuum and non-vacuum techniques. Some methods involve
hazardous chemicals such as hydrazine. An object of the present
invention is to provide a facile, cost-conscious and easily
scalable method for production of kesterite materials of CZTS,
CZTSe or CZTSSe types. It is also an object of the present
invention to provide a non-hazardous production method.
[0004] Moreover, it is an object of the invention to provide a
precursor for a kesterite material of the CZTS, CZTSe or CZTSSe
type for subsequent sulfidation, where the resultant kesterite
material has good efficiency values and/or a high purity.
SUMMARY OF THE INVENTION
[0005] Embodiments of the invention generally relate to a method of
producing a kesterite material of CZTS, CZTSe or CZTSSe type. The
invention moreover relates to a precursor material for a kesterite
material of CZTS, CZTSe or CZTSSe type.
[0006] One embodiment of the invention provides a method producing
a kesterite material of CZTS, CZTSe or CZTSSe type. The method
comprises the steps of:
[0007] a) preparing an acidic solution by dissolving copper and
zinc salts in water in desired molar ratio,
[0008] b) preparing a basic solution by dissolving an alkali metal
stannate together with an alkali metal carbonate or an alkali metal
hydrogen carbonate or an alkali metal hydroxide or a combination
thereof, and optionally with an alkali metal selenate or an alkali
metal selenite or a mixture thereof,
[0009] c) carrying out a precipitation reaction by mixing the
acidic and the basic solution, thereby obtaining a precipitate,
[0010] d) washing and heat treating the precipitate thereby
providing a precursor for the kesterite material, and
[0011] e) sulfurizing the precursor of step d) to provide the
kesterite material.
[0012] In steps a) to d) an essentially sulfur-free precursor
material for a kesterite material is obtained by co-precipitation,
washing and heat treating. In the subsequent step e), the precursor
material obtained by steps a) to d) is sulfided. This method where
the sulfidation takes place at a separate step provides for a
resultant material of higher purity than what is obtained if the
sulfur was introduced from the beginning, e.g. as a metal sulfide,
to provide a basic or alkaline solution for the precipitation
reaction.
[0013] The acidic solution of step a) and the basic solution of
step b) are typically made in distilled or deionized water, and the
pH values thereof are controlled, e.g. by dilution with distilled,
demineralized or de-ionized water. During step c) a precipitate
forms essentially containing the metal components, and optionally
selenium, of the solutions in the predetermined stoichiometry. The
heat treatment in step d) is e.g. carried out by supplying heat to
remove excess washing liquid, e.g. water, and potentially to
convert the precursor to a form that is more suited for
sulfidation, e.g. by decomposing carbonates to oxides. Moreover, if
necessary, further steps may be carried out between step d) and
step e), such as e.g. filtering.
[0014] The identity of the kesterite materials prepared according
to the invention may be proven by using X-ray diffraction (XRD)
and/or Raman spectroscopy (Raman).
[0015] The stoichiometry of the CZTS, CZTSe or CZTSSe phase of the
invention is Cu.sub.2-xZn.sub.1+ySn(S.sub.1-zSe.sub.z).sub.4+q
where 0.ltoreq.x.ltoreq.1; 0.ltoreq.y.ltoreq.1;
0.ltoreq.z.ltoreq.1; -1.ltoreq.q.ltoreq.1. Preferable values for x
lie in the range: 0.ltoreq.x.ltoreq.0.4. Preferable values for y
lie in the range: 0.1.ltoreq.y.ltoreq.0.3. Preferably, the ratio
between (2-x) and (2+y) is in the range:
0.75.ltoreq.(2-x)/(2+y).ltoreq.0.9.
[0016] Advantages of the method are i.a.: [0017] The production
method is aqueous based and does not involve any hazardous
components; [0018] The production method does not imply the use of
vacuum; [0019] The co-precipitation may be conducted at
temperatures below 100.degree. C.; [0020] The production method is
easy to scale up; and [0021] The kesterite material obtained is an
almost phase pure kesterite material, comprising a very low
fraction of copper sulfides, according to Raman spectroscopy.
[0022] In an embodiment the salts used for the acidic solution are
nitrates, halides, sulfates, carboxylates or combinations thereof.
These salts have a substantial solubility in water which is a
prerequisite for the precipitation process of the present
invention.
[0023] In an embodiment the copper salt is copper (II) nitrate and
the zinc salt is zinc (II) nitrate. The nitrate salts have a very
high solubility in water and furthermore, any residual nitrate in
the kesterite precursor will be transformed into gaseous products
during the final sulfidation step. This is preferable to the use of
e.g. halide salts since residual halide ions are more difficult to
remove and will pollute the kesterite phase. The acidic solution
may optionally comprise excess acid, such as nitric acid.
[0024] In an embodiment the alkali metal stannate comprises
Na.sub.2SnO.sub.3 and/or K.sub.2SnO.sub.3 in hydrated or anhydrous
form. In an embodiment, the basic solution further comprises
selenium in the form of an alkali metal selenate and/or an alkali
metal selenite. This provides an easy and accurate method of adding
the selenium part to the kesterite precursor.
[0025] In an embodiment, the step of sulfurizing comprises
subjecting the dried or calcined precursor to a sulfur comprising
gas at a temperature above room temperature. The sulfidation
temperature may e.g. be about 400.degree. C. A kesterite material
with a low content of copper sulfides is obtained (according to
Raman) after the sulfidation, even when sulfidation is carried out
at relatively low temperature, e.g. at about 380.degree. C.
However, preferred sulfidation temperatures lie in the range from
550.degree. C. to 620.degree. C.
[0026] In an embodiment, the sulfur comprising gas is one or more
of the following: H.sub.2S, elemental sulfur in gaseous state
(S.sub.2--S.sub.8), COS, CS.sub.2 and organic sulfur compounds. The
organic sulfur compounds are e.g. CH.sub.3SH and/or
CH.sub.3SSCH.sub.3. Although hydrogen sulfide and/or elemental
sulfur will often be preferred, the potential use of several other
sulfur compounds adds flexibility to the process.
[0027] In an embodiment, the sulfur comprising gas further
comprises selenium. Selenium may thus be introduced as a dopant
either during precipitation or during the post-treatment operation.
Typically, the gaseous selenium is produced on-site, e.g. by
heating of selenium in an inert atmosphere or in a hydrogen
containing atmosphere.
[0028] In an embodiment, the method further comprises the following
steps between steps d) and e): [0029] grinding the precursor for
the kesterite material, [0030] dispersing the grinded precursor in
a liquid, thereby obtaining a slurry, [0031] depositing a thin
layer of the slurry onto a substrate, and [0032] optionally, drying
the thin layer.
[0033] Advantageously, the precursor is grinded and dispersed in a
liquid in order to reduce the particle size and form a slurry that
subsequently is used to produce a thin layer comprising the
precursor on a substrate by standard deposition techniques like
spin coating, doctor-blading, printing, spray coating etc. followed
by a drying step, if needed. The grinding method can be bead
milling or any other standard method used for wet grinding. The
size of all the precursor particles in the slurry should be below
the desired thickness of the thin film. The liquid can be any
solvent like water, ethanol, N-methyl-2-pyrrolidone etc. and also
include dispersion additives as well as other additives. Drying
will typically be done under controlled conditions to avoid cracks
in the dried coat. The step of drying the thin layer could e.g. be
done with heat treatment in an oxidizing atmosphere, such as air or
any other oxygen containing gas or ozone. Hereby, dispersion agent
and binder is removed by oxidation. The precursor layer is
subsequently treated in a gas atmosphere comprising sulfur to form
a uniform thin film of kesterite of CZTS, CZTSe or CZTSSe type. The
method is well-suited to be used to make uniform thin films of
kesterite with few defects (e.g. cracks), such as in photovoltaic
cells.
[0034] In an embodiment, the method further comprises the following
steps after step e): [0035] grinding the kesterite material, [0036]
dispersing the grinded kesterite material in a liquid, thereby
obtaining a slurry, [0037] depositing a thin layer of the slurry
onto a substrate, [0038] optionally, drying the thin layer, and
[0039] optionally, heat treating the thin layer.
[0040] Advantageously, the kesterite material obtained by step e)
is grinded and dispersed in a liquid in order to reduce the
particle size and form a slurry that subsequently is used to form a
thin layer comprising the material on a substrate by standard
deposition techniques like spin coating, doctor-blading, printing,
spray coating etc. followed by drying. The grinding method can be
bead milling or any other standard method used for wet grinding.
The size of all the particles in the slurry should be below the
desired thickness of the thin film. The liquid can be any solvent
like water, ethanol, N-methyl-2-pyrrolidone etc. and also include
dispersion additives as well as other additives. Drying will
typically be done under controlled conditions to avoid cracks in
the dried coat. Heat treatment may be done in a sulfidizing gas to
form a uniform thin film of kesterite of CZTS, CZTSe or CZTSSe
type. The heat treatment of the thin lay may be a two-step heat
treatment, whereof the first step is a heat treatment in an
oxidizing atmosphere, such as air, in order to remove dispersion
agent and binder by oxidation, and the second step is a sulfidation
treatment in order to compensate for any sulfur loss occurring
during the heat treatment in the oxidizing atmosphere.
[0041] The method is well-suited to be used to make uniform thin
films of kesterite with few defects (e.g. cracks), such as in
photovoltaic cells.
[0042] Another aspect of the present invention relates to a
precursor material for a kesterite material of CZTS, CZTSe or
CZTSSe type, where the precursor material is substantially sulfur
free and wherein powder XRD shows that the precursor material
comprises a Zn[Sn(OH).sub.6] phase and/or a Cu[Sn(OH).sub.6] phase
and/or a mixed {Cu, Zn}[Sn(OH).sub.6] phase. This intimate mixing
of the metals allows for easy and swift sulfidation and plays an
important role in obtaining a practically phase pure CZTS, CZTSe or
CZTSSe material after sulfidation. Consequently, a CZTS, CZTSe or
CZTSSe type kesterite material prepared from the precursor material
has a high purity. Thus, on sulfidation of the precursor, an almost
phase pure kesterite material is achieved, comprising a very low
fraction of copper sulfides, according to Raman spectroscopy.
[0043] In an embodiment, the kesterite material has a crystal size
of 10-200 nm and a lattice constant a=5.438.+-.0.5 .ANG. and
c=10.839.+-.1.0 .ANG..
EXAMPLES
Example 1a. Preparation of a CZTS Hydroxy Carbonate Precursor
[0044] Two solutions were prepared: An acidic solution (solution A)
and a basic solution (solution B).
[0045] Solution A was prepared by mixing 189.1 g of a copper
nitrate solution which was analyzed to contain 16.8% wt/wt Cu (0.50
mol Cu) with 66 g of 65% HNO.sub.3 (0.65 mol) and then adding 20.3
g of solid ZnO (0.25 mol) and diluting the resulting solution to
1.5 liter with deionized water.
[0046] Solution B was prepared by adding 74.7 g
K.sub.2SnO.sub.3*3H.sub.2O (0.25 mol) to 241 g of a 33% wt/wt
solution of K.sub.2CO.sub.3 (0.575 mol) and diluting the suspension
to 1.5 liter with deionized water.
[0047] When almost all solids had dissolved (solution B does not
become completely transparent), solution A and solution B were
mixed in a large beaker which was mechanically stirred. The two
solutions were simultaneously pumped into the beaker at constant
and almost equal flow rates. pH was measured throughout this step
and it was found to be fairly constant at approximately 6.5. After
the two solutions had been mixed, the resultant blue precipitate
was ripened by heating to 70.degree. C. and keeping the temperature
at 70.degree. C. for one half hour. The product was filtered off,
washed several times with hot, demineralized water and dried in an
oven at 100.degree. C. for 3 days.
[0048] XRD analysis (Rietveld refinement) of this material showed a
Zn[Sn(OH).sub.6] phase with average crystal size D=280 .ANG. and
lattice constant a=7.78 .ANG. together with an amorphous phase. No
copper-containing phase was detected.
Example 1b. Preparation of CZTS Material
[0049] The dried precursor obtained in Example 1a was sulfided in
the following way. A sieved fraction of the precursor (0.15-0.30
mm) was used. A total of 0.5 g was loaded into a tubular reactor
and heated to 380.degree. C. in a stream of N.sub.2 containing 100
ppm H.sub.2S. The sulfur uptake was determined by gas chromatograph
measurements. When the sample did not take up any more sulfur, the
treatment was disrupted and the sample was cooled to ambient
temperature.
[0050] The resultant black material was analyzed by XRD and Raman
spectroscopy. XRD analysis (Rietveld refinement) showed phase pure
Cu.sub.2ZnSnS.sub.4 with average crystal size D=446 .ANG. and
lattice constants a=5.438 .ANG. and c=10.839 .ANG.. Raman
spectroscopy showed a single Raman shift at 327 cm.sup.-1.
Example 2. Preparation of CZTS Film Based on Sulfur Free CZTS
Precursor
[0051] A CZTS precursor was prepared as described in Example la
with the exception that Cu:Zn:Sn ratio is 1.76:1.20:1.00. This
precursor was heat treated in stagnant air at 350.degree. C. for 4
h in order to transform the precursor into a Cu--Zn--Sn oxide
precursor. A slurry for coating the Cu--Zn--Sn oxide precursor was
prepared in the following way. 5 g ethanol (EtOH), 2 g of a
VOC-free structured acrylic copolymer dispersion agent and 1 g of a
polyvinylbutyral-based binder was added to a 50 ml PE bottle
together with 30 g of ZrO.sub.2 pearls, o 1.5 mm and shaken in a
paint shaker for 2 min. 10 g of the Cu--Zn--Sn oxide precursor was
added and the slurry was further shaken for 600 min in the paint
shaker. Diffuse reflectance spectroscopy was used to determine that
90% of the volume weighted particle size distribution was below 1
.mu.m after this. Some of the slurry was applied as a thin layer
onto a piece of soda-lime glass and dried in ambient air. By
scanning electron spectroscopy, it was verified that the coated
layer was approximately 1-2 .mu.m thick, homogeneous and
essentially free of large cracks. The coated soda-lime glass was
then treated in a stream of nitrogen containing 10 vol % H.sub.2S
at a temperature of 600.degree. C., in order to transform the
precursor film into a CZTS film. The optical quality of the film
was checked by photoluminescence. The photoluminescence from the
film had maximum intensity at a photon energy of 1.37 eV and the
peak had a FWHM of 0.26 eV which indicates that a good quality CZTS
with relative few defects that would be detrimental to the
performance of a solar cell based on the material.
Example 3. Preparation of CZTS Film Based on CZTS Powder
[0052] A CZTS powder was prepared as described in Example 1b with
the exception that it was sulfided in a stream of nitrogen
containing 10 vol % H.sub.2S at 620.degree. C. for 2 h. A slurry
for coating this CZTS powder was prepared in the following way. 1.5
g EtOH, 0.6 g a VOC-free structured acrylic copolymer dispersion
agent and 0.3 g of a polyvinylbutyral-based binder was added to a
10 ml PE bottle together with 9 g of ZrO.sub.2 pearls, o 1.5 mm and
shaken in a paint shaker for 2 min. 3 g of CZTS powder was added
and the slurry was further shaken for 180 min in the paint shaker.
Diffuse reflectance spectroscopy was used to determine that 90% of
the volume weighted particle size distribution was below 1 .mu.m
after this. Some of the slurry was applied as a thin layer onto a
piece of soda-lime glass and dried in ambient air. By scanning
electron spectroscopy, it was verified that the coated layer was
approximately 1-2 .mu.m thick, homogeneous and essentially free of
large cracks. The optical quality of the film was checked by
photoluminescence. The photo luminescence from the film had maximum
intensity at a photon energy of 1.37 eV and the peak had a FWHM of
0.28 eV which indicates that a good quality CZTS with relative few
defects that would be detrimental to the performance of a solar
cell based on the material.
[0053] While the invention has been illustrated by a description of
various embodiments and while these embodiments have been described
in detail, it is not the intention of the applicant to restrict or
in any way limit the scope of the appended claims to such detail.
Additional advantages and modifications will readily appear to
those skilled in the art. The invention in its broader aspects is
therefore not limited to the specific details, representative
methods, and illustrative examples shown and described.
Accordingly, departures may be made from such details without
departing from the spirit or scope of applicant's general inventive
concept.
* * * * *